This study presents a skin-conformal and breathable humidity sensor for emotional mode recognition and non-contact human-machine interface applications. The sensor, assembled by anchoring MXenes-based composite into electrospun elastomer nanofibers coated with a patterned electrode, exhibits excellent air permeability, high sensitivity, and fast response/recovery. Its skin conformability and biocompatibility allow for comfortable long-term use, enabling the recognition of motional states and emotional modes through humidity fluctuation.